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Title: Determination of the structural phase and octahedral rotation angle in halide perovskites

Abstract

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). Finally, the approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [2];  [2];  [2];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center for Electron Microscopy, Molecular Foundry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1434015
Alternate Identifier(s):
OSTI ID: 1420206
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Applied Physics Letters
Additional Journal Information:
Journal Volume: 112; Journal Issue: 7; Journal ID: ISSN 0003-6951
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

dos Reis, Roberto, Yang, Hao, Ophus, Colin, Ercius, Peter, Bizarri, Gregory, Perrodin, Didier, Shalapska, Tetiana, Bourret, Edith, Ciston, Jim, and Dahmen, Ulrich. Determination of the structural phase and octahedral rotation angle in halide perovskites. United States: N. p., 2018. Web. doi:10.1063/1.5017537.
dos Reis, Roberto, Yang, Hao, Ophus, Colin, Ercius, Peter, Bizarri, Gregory, Perrodin, Didier, Shalapska, Tetiana, Bourret, Edith, Ciston, Jim, & Dahmen, Ulrich. Determination of the structural phase and octahedral rotation angle in halide perovskites. United States. doi:10.1063/1.5017537.
dos Reis, Roberto, Yang, Hao, Ophus, Colin, Ercius, Peter, Bizarri, Gregory, Perrodin, Didier, Shalapska, Tetiana, Bourret, Edith, Ciston, Jim, and Dahmen, Ulrich. Mon . "Determination of the structural phase and octahedral rotation angle in halide perovskites". United States. doi:10.1063/1.5017537. https://www.osti.gov/servlets/purl/1434015.
@article{osti_1434015,
title = {Determination of the structural phase and octahedral rotation angle in halide perovskites},
author = {dos Reis, Roberto and Yang, Hao and Ophus, Colin and Ercius, Peter and Bizarri, Gregory and Perrodin, Didier and Shalapska, Tetiana and Bourret, Edith and Ciston, Jim and Dahmen, Ulrich},
abstractNote = {A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). Finally, the approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.},
doi = {10.1063/1.5017537},
journal = {Applied Physics Letters},
number = 7,
volume = 112,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

FIG. 1 FIG. 1: Possible crystal structures of CsPbBr3 following the group-subgroup relationship for perovskites. (a) Cubic Pm $\bar{3}$m, the aristotype crystal, denoted by Glazer notation a0a0a0. (b) Tetragonal phase P4/mbm generated by in-phase rotation P4/mbm denoted by a0a0c+. (c) Tetragonal, I4/mcm generated by out-of-phase rotation, denoted by a0a0c- . (d) Pnmamore » structure viewed along in-plane, [010]O, and out of plane [101]O of the pseudocubic axis of the orthorhombic structure.« less

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